Scanning probe microscopy in probing low-dimensional carbon-based nanostructures and nanomaterials

doi: 10.1088/2752-5724/ac8a63

Interdisciplinary Materials Research Center, College of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China

More Information

Corresponding author: E-mail: xuwei@tongji.edu.cn

摘要

Abstract: Carbon, as an indispensable chemical element on Earth, has diverse covalent bonding ability, which enables construction of extensive pivotal carbon-based structures in multiple scientific fields. The extraordinary physicochemical properties presented by pioneering synthetic carbon allotropes, typically including fullerenes, carbon nanotubes, and graphene, have stimulated broad interest in fabrication of carbon-based nanostructures and nanomaterials. Accurate regulation of topology, size, and shape, as well as controllably embedding target spⁿ-hybridized carbons in molecular skeletons, is significant for tailoring their structures and consequent properties and requires atomic precision in their preparation. Scanning probe microscopy (SPM), combined with on-surface synthesis strategy, has demonstrated its capabilities in fabrication of various carbon-based nanostructures and nanomaterials with atomic precision, which has long been elusive for conventional solution-phase synthesis due to realistic obstacles in solubility, isolation, purification, etc. More intriguingly, atom manipulation via an SPM tip allows unique access to local production of highly reactive carbon-based nanostructures. In addition, SPM provides topographic information of carbon-based nanostructures as well as their characteristic electronic structures with unprecedented submolecular resolution in real space. In this review, we overview recent exciting progress in the delicate application of SPM in probing low-dimensional carbon-based nanostructures and nanomaterials, which will open an avenue for the exploration and development of elusive and undiscovered carbon-based nanomaterials.
- scanning probe microscopy /
- carbon nanostructures /
- carbon nanomaterials /
- synthetic carbon allotropes /
- on-surface synthesis
注释:

HTML全文

下载: 全尺寸图片幻灯片

Figure 1. Schematic illustration showing the application of SPM techniques in the exploration of carbon-based nanostructures and nanomaterials on surfaces.

下载: 全尺寸图片幻灯片

Figure 2. On-surface synthesis and characterization of 0D nanostructures, including fullerenes and cyclo[18]carbons. (a) Synthesis of triazafullerene C₅₇N₃ on Pt(111) and corresponding STM characterization. Reproduced from [24], with permission from Springer Nature. (b) AFM characterization of C₆₀ on a (101) anatase surface with intramolecular resolution using a multipass method. Reprinted with permission from [32]. Copyright (2015) American Chemical Society. (c) In-situ generation of cyclo[18]carbon by atom manipulation and subsequent structural characterization. From [22]. Reprinted with permission from AAAS.

下载: 全尺寸图片幻灯片

Figure 3. On-surface synthesis and characterization of 0D nanographenes in small sizes. (a) Synthesis and STM/STS/nc-AFM characterization of dibenzoperioctacenes on Au(111). Reproduced from [42]. CC BY 4.0. (b) Fabrication of a C108 cycloarene on Au(111). Reprinted with permission from [52]. Copyright (2020) American Chemical Society. (c) Synthesis and characterization of [6]- and [5]coronoids on Au(111). (d) Z-dependent nc-AFM images of a [5]coronoid. (c), (d) Reproduced from [53]. CC BY 4.0. (e) Reaction process and intermediate states detected in the formation of biphenylene dimers on Ag(111). Reprinted with permission from [55]. Copyright (2022) American Chemical Society.

下载: 全尺寸图片幻灯片

Figure 4. On-surface synthesis and characterization of graphene-related oligomers and macrocycles. (a) Chemical structure; (b) constant-height dI/dV map characterization with a CO-tip; and (c) constant-height dI/dV map (at 2.4 V) of nanographenes (C₁₈₆H₆₀) with azulene moieties embedded on Au(111). Scale bar in (b): 1.2 nm. Reprinted with permission from [67]. Copyright (2018) American Chemical Society. (d) Synthetic route and (e) skeletal characterization of a triangulene-based nanostar. (f) dI/dV spectra acquired at the edge of a triangulene unit on Au(111) as marked by the blue dot in (e). (g) Stacked dI/dV plot along the line AB depicted in (e). (d)-(g) [79] John Wiley & Sons. [© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH]. (h) Synthesis and (i) skeletal characterization of a covalently linked organic quantum corral on Au(111). Scale bar: 5 Å. (j) dI/dV spectra acquired at different sites inside the organic quantum corral on Au(111). (k) dI/dV maps characterizing the quantum resonance states trapped inside the organic corral. Scale bar: 1 nm. (h)-(k) Reproduced from [81]. CC BY 4.0.

下载: 全尺寸图片幻灯片

Figure 5. On-surface synthesis of polyacetylene, polyene, and polyethylene. (a) Dehydrogenation of n-alkanes to produce all-trans conjugated polyene on Cu(110). Reproduced from [95]. CC BY 4.0. (b) Coupling reaction of conjugated polyenes on Cu(110) with the formation of polyacetylene containing three different connections. Reproduced from [96], with permission from Springer Nature. (c) Polymerization of ethylene on a carburized iron single-crystal surface at RT. (d) An individual C₂H₄ molecule (left) and ethylidene (CHCH₃, right) captured by LT-STM imaging. (e) Polymer chain growth forming C₈ and C₁₀ chains. (c)-(e) From [97]. Reprinted with permission from AAAS.

下载: 全尺寸图片幻灯片

Figure 6. On-surface synthesis and characterization of a series of polyacetylenes, organometallic and intrinsic polyynes. (a)-(e) Synthesis and characterization of cis- and trans-polyacetylenes and Cu-carbyne on Cu(110) by applying C₂H₂ as precursor. (b)-(d) Reproduced from [105], with permission from Springer Nature. (e) Reprinted with permission from [101]. Copyright (2016) American Chemical Society. (f)-(i) Synthesis and characterization of 1D diacetylenic Au-carbyne on Au(111). (g)-(i) Reprinted with permission from [102]. Copyright (2020) American Chemical Society. (j) Triacetylenic Ag-carbyne on Ag(111). Reprinted with permission from [103]. Copyright (2022) American Chemical Society. (k) In-situ synthesis of polyynes on NaCl/Cu(111). Reproduced from [23], with permission from Springer Nature.

下载: 全尺寸图片幻灯片

Figure 7. On-surface synthesis and characterization of graphene nanoribbons including sGNR and 5-sGNR. (a) Synthesis of 5-sGNR on Au(111) from molecular precursor 1 with the formation of sGNR as an intermediate state. (b)-(d) STM images of (b) molecular precursor 1, (c) an isolated sGNR, and (d) 5-sGNR on Au(111). (e) dI/dV spectra and mapping of 5-sGNR on Au(111). State 1, state 3, and state 2 showed the valence band, conduction band, and zero-mode band, respectively. From [118]. Reprinted with permission from AAAS.

下载: 全尺寸图片幻灯片

Figure 8. On-surface synthesis and characterization of 1D -conjugated polymers. (a) Synthesis of -conjugated polymers comprising bisanthene units. (b) Nc-AFM image resolving the chain skeletons. (c) dI/dV spectra conducted at the corresponding positions marked in (b). (d) dI/dV mapping and simulations obtained at the edges of valence band and conduction band. (e) dI/dV spectra showing the distribution of the edge state. The sequence from top to bottom corresponds to the sites from the termination of the polymer to the center. (f) Nc-AFM and STM images of the -conjugated polymer. Reproduced from [157], with permission from Springer Nature.

下载: 全尺寸图片幻灯片

Figure 9. Schematic illustration of the prospect of SPM techniques in probing low-dimensional carbon-based nanostructures and nanomaterials.

下载: 全尺寸图片幻灯片

参考文献(194)

[1]	Hirsch A 2010 The era of carbon allotropes Nat. Mater. 9 868-71 doi: 10.1038/nmat2885
[2]	Kroto H W, Heath J R, O’Brien S C, Curl R F, Smalley R E 1985 C₆₀: buckminsterfullerene Nature 318 162-3 doi: 10.1038/318162a0
[3]	Iijima S 1991 Helical microtubules of graphitic carbon Nature 354 56-58 doi: 10.1038/354056a0
[4]	Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y, Dubonos S V, Grigorieva I V, Firsov A A 2004 Electric field effect in atomically thin carbon films Science 306 666-9 doi: 10.1126/science.1102896
[5]	Bottari G, Torres T 2017 A new dimension for low-dimensional carbon nanostructures Chem 3 21-24 doi: 10.1016/j.chempr.2017.06.012
[6]	Li G, Li Y, Liu H, Guo Y, Li Y, Zhu D 2010 Architecture of graphdiyne nanoscale films Chem. Commun. 46 3256-8 doi: 10.1039/b922733d
[7]	Li Y, Xu L, Liu H, Li Y 2014 Graphdiyne and graphyne: from theoretical predictions to practical construction Chem. Soc. Rev. 43 2572-86 doi: 10.1039/c3cs60388a
[8]	Gao X, Liu H, Wang D, Zhang J 2019 Graphdiyne: synthesis, properties, and applications Chem. Soc. Rev. 48 908-36 doi: 10.1039/C8CS00773J
[9]	Chalifoux W A, Tykwinski R R 2010 Synthesis of polyynes to model the sp-carbon allotrope carbyne Nat. Chem. 2 967-71 doi: 10.1038/nchem.828
[10]	Liu M, Artyukhov V I, Lee H, Xu F, Yakobson B I 2013 Carbyne from first principles: chain of C atoms, a nanorod or a nanorope ACS Nano 7 10075-82 doi: 10.1021/nn404177r
[11]	Tongay S, Senger R T, Dag S, Ciraci S 2004 Ab-initio electron transport calculations of carbon based string structures Phys. Rev. Lett. 93 136404 doi: 10.1103/PhysRevLett.93.136404
[12]	Li X, Zhang H, Chi L 2018 On-surface synthesis of graphyne-based nanostructures Adv. Mater. 31 1804087 doi: 10.1002/adma.201804087
[13]	Chen H, Zhu H, Huang Z, Rong W, Wu K 2019 Two-sidedness of surface reaction mediation Adv. Mater. 31 1902080 doi: 10.1002/adma.201902080
[14]	Shen Q, Gao H-Y, Fuchs H 2017 Frontiers of on-surface synthesis: from principles to applications Nano Today 13 77-96 doi: 10.1016/j.nantod.2017.02.007
[15]	Grill L, Hecht S 2020 Covalent on-surface polymerization Nat. Chem. 12 115-30 doi: 10.1038/s41557-019-0392-9
[16]	Dong L, Liu P N, Lin N 2015 Surface-activated coupling reactions confined on a surface Acc. Chem. Res. 48 2765-74 doi: 10.1021/acs.accounts.5b00160
[17]	Klappenberger F, Zhang Y-Q, Bjrk J, Klyatskaya S, Ruben M, Barth J V 2015 On-surface synthesis of carbon-based scaffolds and nanomaterials using terminal alkynes Acc. Chem. Res. 48 2140-50 doi: 10.1021/acs.accounts.5b00174
[18]	Held P A, Fuchs H, Studer A 2017 Covalent-bond formation via on-surface chemistry Chem. Eur. J. 23 5874-92 doi: 10.1002/chem.201604047
[19]	Clair S, de Oteyza D G 2019 Controlling a chemical coupling reaction on a surface: tools and strategies for on-surface synthesis Chem. Rev. 119 4717-76 doi: 10.1021/acs.chemrev.8b00601
[20]	Bian K, Gerber C, Heinrich A J, Mller D J, Scheuring S, Jiang Y 2021 Scanning probe microscopy Nat. Rev. Methods Primers 1 36 doi: 10.1038/s43586-021-00033-2
[21]	Gross L, Schuler B, Pavliek N, Fatayer S, Majzik Z, Moll N, Pea D, Meyer G 2018 Atomic force microscopy for molecular structure elucidation Angew. Chem., Int. Ed. 57 3888-908 doi: 10.1002/anie.201703509
[22]	Kaiser K, Scriven L M, Schulz F, Gawel P, Gross L, Anderson H L 2019 An sp-hybridized molecular carbon allotrope, cyclo[18]carbon Science 365 1299-301 doi: 10.1126/science.aay1914
[23]	Pavliek N, Gawel P, Kohn D R, Majzik Z, Xiong Y, Meyer G, Anderson H L, Gross L 2018 Polyyne formation via skeletal rearrangement induced by atomic manipulation Nat. Chem. 10 853-8 doi: 10.1038/s41557-018-0067-y
[24]	Otero G, et al 2008 Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation Nature 454 865-8 doi: 10.1038/nature07193
[25]	Amsharov K, Abdurakhmanova N, Stepanow S, Rauschenbach S, Jansen M, Kern K 2010 Towards the isomer-specific synthesis of higher fullerenes and buckybowls by the surface-catalyzed cyclodehydrogenation of aromatic precursors Angew. Chem., Int. Ed. 49 9392-6 doi: 10.1002/anie.201005000
[26]	Pinardi A L, et al 2013 Tailored formation of N-doped nanoarchitectures by diffusion-controlled on-surface (cyclo)-dehydrogenation of heteroaromatics ACS Nano 7 3676-84 doi: 10.1021/nn400690e
[27]	Pinardi A L, Martnez J I, Janak A, Star I G, Star I, Lpez M F, Mndez J, Martn-Gago J 2014 Sequential formation of N-doped nanohelicenes, nanographenes and nanodomes by surface-assisted chemical (cyclo)dehydrogenation of heteroaromatics Chem. Commun. 50 1555-7 doi: 10.1039/c3cc47399f
[28]	Lu J, Yeo P S E, Gan C K, Wu P, Loh K P 2011 Transforming C₆₀ molecules into graphene quantum dots Nat. Nanotechnol. 6 247-52 doi: 10.1038/nnano.2011.30
[29]	Gross L, Mohn F, Moll N, Liljeroth P, Meyer G 2009 The chemical structure of a molecule resolved by atomic force microscopy Science 325 1110-4 doi: 10.1126/science.1176210
[30]	Giessibl F J 2019 The qPlus sensor, a powerful core for the atomic force microscope Rev. Sci. Instrum. 90 11101 doi: 10.1063/1.5052264
[31]	Gross L, Mohn F, Moll N, Schuler B, Criado A, Guitin E, Pea D, Gourdon A, Meyer G 2012 Bond-order discrimination by atomic force microscopy Science 337 1326-9 doi: 10.1126/science.1225621
[32]	Moreno C, Stetsovych O, Shimizu T K, Custance O 2015 Imaging three-dimensional surface objects with submolecular resolution by atomic force microscopy Nano Lett. 15 2257-62 doi: 10.1021/nl504182w
[33]	Scriven L M, Kaiser K, Schulz F, Sterling A J, Woltering S L, Gawel P, Christensen K E, Anderson H L, Gross L 2020 Synthesis of cyclo[18]carbon via debromination of C₁₈Br₆ J. Am. Chem. Soc. 142 12921-4 doi: 10.1021/jacs.0c05033
[34]	Mllen K, Rabe J P 2008 Nanographenes as active components of single-molecule electronics and how a scanning tunneling microscope puts them to work Acc. Chem. Res. 41 511-20 doi: 10.1021/ar7001446
[35]	Fujii S, Enoki T 2013 Nanographene and graphene edges: electronic structure and nanofabrication Acc. Chem. Res. 46 2202-10 doi: 10.1021/ar300120y
[36]	Son Y-W, Cohen M L, Louie S G 2006 Energy gaps in graphene nanoribbons Phys. Rev. Lett. 97 216803 doi: 10.1103/PhysRevLett.97.216803
[37]	Zuzak R, et al 2018 Building a 22-ring nanographene by combining in-solution and on-surface syntheses Chem. Commun. 54 10256-9 doi: 10.1039/C8CC05353G
[38]	Mishra S, Beyer D, Berger R, Liu J, Grning O, Urgel J I, Mllen K, Ruffieux P, Feng X, Fasel R 2020 Topological defect-induced magnetism in a nanographene J. Am. Chem. Soc. 142 1147-52 doi: 10.1021/jacs.9b09212
[39]	Rogers C, Chen C, Pedramrazi Z, Omrani A A, Tsai H-Z, Jung H S, Lin S, Crommie M F, Fischer F R 2015 Closing the nanographene gap: surface-assisted synthesis of peripentacene from 6,6ʹ-bipentacene precursors Angew. Chem., Int. Ed. 54 15143-6 doi: 10.1002/anie.201507104
[40]	Wang X-Y, et al 2017 Heteroatom-doped perihexacene from a double helicene precursor: on-surface synthesis and properties J. Am. Chem. Soc. 139 4671-4 doi: 10.1021/jacs.7b02258
[41]	Telychko M, et al 2021 Ultrahigh-yield on-surface synthesis and assembly of circumcoronene into a chiral electronic Kagome-honeycomb lattice Sci. Adv. 7 eabf0269 doi: 10.1126/sciadv.abf0269
[42]	Zhong Q, et al 2019 Benzo-fused periacenes or double helicenes? Different cyclodehydrogenation pathways on surface and in solution J. Am. Chem. Soc. 141 7399-406 doi: 10.1021/jacs.9b01267
[43]	Hu Y, Wang X-Y, Peng P-X, Wang X-C, Cao X-Y, Feng X, Mllen K, Narita A 2017 Benzo-fused double [7]carbohelicene: synthesis, structures, and physicochemical properties Angew. Chem., Int. Ed. 56 3374-8 doi: 10.1002/anie.201610434
[44]	Mishra S, Lohr T G, Pignedoli C A, Liu J, Berger R, Urgel J I, Mllen K, Feng X, Ruffieux P, Fasel R 2018 Tailoring bond topologies in open-shell graphene nanostructures ACS Nano 12 11917-27 doi: 10.1021/acsnano.8b07225
[45]	Mishra S, et al 2020 Topological frustration induces unconventional magnetism in a nanographene Nat. Nanotechnol. 15 22-28 doi: 10.1038/s41565-019-0577-9
[46]	Mishra S, et al 2021 Large magnetic exchange coupling in rhombus-shaped nanographenes with zigzag periphery Nat. Chem. 13 581-6 doi: 10.1038/s41557-021-00678-2
[47]	Buttrick J C, King B T 2017 Kekulenes, cycloarenes, and heterocycloarenes: addressing electronic structure and aromaticity through experiments and calculations Chem. Soc. Rev. 46 7-20 doi: 10.1039/C6CS00174B
[48]	Pozo I, Majzik Z, Pavliek N, Melle-Franco M, Guitin E, Pea D, Gross L, Prez D 2019 Revisiting kekulene: synthesis and single-molecule imaging J. Am. Chem. Soc. 141 15488-93 doi: 10.1021/jacs.9b07926
[49]	Treier M, Pignedoli C A, Laino T, Rieger R, Mllen K, Passerone D, Fasel R 2011 Surface-assisted cyclodehydrogenation provides a synthetic route towards easily processable and chemically tailored nanographenes Nat. Chem. 3 61-67 doi: 10.1038/nchem.891
[50]	Su J, Wu X, Song S, Telychko M, Lu J 2020 Substrate induced strain for on-surface transformation and synthesis Nanoscale 12 7500-8 doi: 10.1039/D0NR01270J
[51]	Shiotari A, Nakae T, Iwata K, Mori S, Okujima T, Uno H, Sakaguchi H, Sugimoto Y 2017 Strain-induced skeletal rearrangement of a polycyclic aromatic hydrocarbon on a copper surface Nat. Commun. 8 16089 doi: 10.1038/ncomms16089
[52]	Fan Q, Martin-Jimenez D, Werner S, Ebeling D, Koehler T, Vollgraff T, Sundermeyer J, Hieringer W, Schirmeisen A, Gottfried J M 2020 On-surface synthesis and characterization of a cycloarene: C₁₀₈ graphene ring J. Am. Chem. Soc. 142 894-9 doi: 10.1021/jacs.9b10151
[53]	Di Giovannantonio M, Yao X, Eimre K, Urgel J I, Ruffieux P, Pignedoli C A, Mllen K, Fasel R, Narita A 2020 Large-cavity coronoids with different inner and outer edge structures J. Am. Chem. Soc. 142 12046-50 doi: 10.1021/jacs.0c05268
[54]	Xu K, et al 2019 On-surface synthesis of a nonplanar porous nanographene J. Am. Chem. Soc. 141 7726-30 doi: 10.1021/jacs.9b03554
[55]	Zeng Z, et al 2022 Chemisorption-induced formation of biphenylene dimer on Ag(111) J. Am. Chem. Soc. 144 723-32 doi: 10.1021/jacs.1c08284
[56]	Zhang C, Kazuma E, Kim Y 2019 Atomic-scale visualization of the stepwise metal-mediated dehalogenative cycloaddition reaction pathways: competition between radicals and organometallic intermediates Angew. Chem., Int. Ed. 58 17736-44 doi: 10.1002/anie.201909111
[57]	Li Q, Gao J, Li Y, Fuentes-Cabrera M, Liu M, Qiu X, Lin H, Chi L, Pan M 2018 Self-assembly directed one-step synthesis of [4]radialene on Cu(100) surfaces Nat. Commun. 9 3113 doi: 10.1038/s41467-018-05472-2
[58]	Liu J, et al 2019 Open-shell non-benzenoid nanographenes containing two pairs of pentagonal and heptagonal rings J. Am. Chem. Soc. 141 12011-20 doi: 10.1021/jacs.9b04718
[59]	Lohr T G, et al 2020 On-surface synthesis of non-benzenoid nanographenes by oxidative ring-closure and ring-rearrangement reactions J. Am. Chem. Soc. 142 13565-72 doi: 10.1021/jacs.0c05668
[60]	Mallada B, et al 2021 On-surface strain-driven synthesis of nonalternant non-benzenoid aromatic compounds containing four- to eight-membered rings J. Am. Chem. Soc. 143 14694-702 doi: 10.1021/jacs.1c06168
[61]	Stetsovych O, vec M, Vacek J, Chocholouov J V, Janak A, Rybek J, Kosmider K, Star I G, Jelnek P, Stary I 2017 From helical to planar chirality by on-surface chemistry Nat. Chem. 9 213-8 doi: 10.1038/nchem.2662
[62]	Bischoff F, Riss A, Michelitsch G S, Ducke J, Barth J V, Reuter K, Auwrter W 2021 Surface-mediated ring-opening and porphyrin deconstruction via conformational distortion J. Am. Chem. Soc. 143 15131-8 doi: 10.1021/jacs.1c05348
[63]	Kawai S, et al 2016 Thermal control of sequential on-surface transformation of a hydrocarbon molecule on a copper surface Nat. Commun. 7 12711 doi: 10.1038/ncomms12711
[64]	Kawai S, et al 2017 Competing annulene and radialene structures in a single anti-aromatic molecule studied by high-resolution atomic force microscopy ACS Nano 11 8122-30 doi: 10.1021/acsnano.7b02973
[65]	Nakamura K, Li Q-Q, Krej O, Foster A S, Sun K, Kawai S, Ito S 2020 On-surface synthesis of a -extended diaza[8]circulene J. Am. Chem. Soc. 142 11363-9 doi: 10.1021/jacs.0c02534
[66]	Mishra S, Fatayer S, Fernndez S, Kaiser K, Pea D, Gross L 2022 Nonbenzenoid high-spin polycyclic hydrocarbons generated by atom manipulation ACS Nano 16 3264-71 doi: 10.1021/acsnano.1c11157
[67]	Hieulle J, Carbonell-Sanrom E, Vilas-Varela M, Garcia-Lekue A, Guitin E, Pea D, Pascual J I 2018 On-surface route for producing planar nanographenes with azulene moieties Nano Lett. 18 418-23 doi: 10.1021/acs.nanolett.7b04309
[68]	Hou I C-Y, Sun Q, Eimre K, Di Giovannantonio M, Urgel J I, Ruffieux P, Narita A, Fasel R, Mllen K 2020 On-surface synthesis of unsaturated carbon nanostructures with regularly fused pentagon-heptagon pairs J. Am. Chem. Soc. 142 10291-6 doi: 10.1021/jacs.0c03635
[69]	Su J, Telychko M, Song S, Lu J 2020 Triangulenes: from precursor design to on-surface synthesis and characterization Angew. Chem., Int. Ed. 59 7658-68 doi: 10.1002/anie.201913783
[70]	Pavliek N, Mistry A, Majzik Z, Moll N, Meyer G, Fox D J, Gross L 2017 Synthesis and characterization of triangulene Nat. Nanotechnol. 12 308-11 doi: 10.1038/nnano.2016.305
[71]	Mishra S, et al 2019 Synthesis and characterization of -extended triangulene J. Am. Chem. Soc. 141 10621-5 doi: 10.1021/jacs.9b05319
[72]	Su J, et al 2019 Atomically precise bottom-up synthesis of -extended [5]triangulene Sci. Adv. 5 eaav7717 doi: 10.1126/sciadv.aav7717
[73]	Mishra S, Xu K, Eimre K, Komber H, Ma J, Pignedoli C A, Fasel R, Feng X, Ruffieux P 2021 Synthesis and characterization of [7]triangulene Nanoscale 13 1624-8 doi: 10.1039/D0NR08181G
[74]	Su J, et al 2021 On-surface synthesis and characterization of [7]triangulene quantum ring Nano Lett. 21 861-7 doi: 10.1021/acs.nanolett.0c04627
[75]	Mishra S, et al 2020 Collective all-carbon magnetism in triangulene dimers Angew. Chem., Int. Ed. 59 12041-7 doi: 10.1002/anie.202002687
[76]	Cheng S, Xue Z, Li C, Liu Y, Xiang L, Ke Y, Yan K, Wang S, Yu P 2022 On-surface synthesis of triangulene trimers via dehydration reaction Nat. Commun. 13 1705 doi: 10.1038/s41467-022-29371-9
[77]	Mishra S, et al 2021 Observation of fractional edge excitations in nanographene spin chains Nature 598 287-92 doi: 10.1038/s41586-021-03842-3
[78]	Wang T, Berdonces-Layunta A, Friedrich N, Vilas-Varela M, Calupitan J P, Pascual J I, Pea D, Casanova D, Corso M, de Oteyza D G 2022 Aza-triangulene: on-surface synthesis and electronic and magnetic properties J. Am. Chem. Soc. 144 4522-9 doi: 10.1021/jacs.1c12618
[79]	Hieulle J, et al 2021 On-surface synthesis and collective spin excitations of a triangulene-based nanostar Angew. Chem., Int. Ed. 60 25224-9 doi: 10.1002/anie.202108301
[80]	Song S, Su J, Telychko M, Li J, Li G, Li Y, Su C, Wu J, Lu J 2021 On-surface synthesis of graphene nanostructures with -magnetism Chem. Soc. Rev. 50 3238-62 doi: 10.1039/D0CS01060J
[81]	Peng X, et al 2021 Visualizing designer quantum states in stable macrocycle quantum corrals Nat. Commun. 12 5895 doi: 10.1038/s41467-021-26198-8
[82]	Labinger J A, Bercaw J E 2002 Understanding and exploiting C-H bond activation Nature 417 507-14 doi: 10.1038/417507a
[83]	Kruppe C M, Krooswyk J D, Trenary M 2017 Selective hydrogenation of acetylene to ethylene in the presence of a carbonaceous surface layer on a Pd/Cu(111) single-atom alloy ACS Catal. 7 8042-9 doi: 10.1021/acscatal.7b02862
[84]	Molina D L, Muir M, Abdel-Rahman M K, Trenary M 2021 The influence of palladium on the hydrogenation of acetylene on Ag(111) J. Chem. Phys. 154 184701 doi: 10.1063/5.0050587
[85]	Shilov A E, Shul’pin G B 1997 Activation of C-H bonds by metal complexes Chem. Rev. 97 2879-923 doi: 10.1021/cr9411886
[86]	Marcinkowski M D, Darby M T, Liu J, Wimble J M, Lucci F R, Lee S, Michaelides A, Flytzani-Stephanopoulos M, Stamatakis M, Sykes E C H 2018 Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation Nat. Chem. 10 325-32 doi: 10.1038/nchem.2915
[87]	Rabe J P, Buchholz S 1991 Commensurability and mobility in two-dimensional molecular patterns on graphite Science 253 424-7 doi: 10.1126/science.253.5018.424
[88]	Askadskaya L, Rabe J P 1992 Anisotropic molecular dynamics in the vicinity of order-disorder transitions in organic monolayers Phys. Rev. Lett. 69 1395-8 doi: 10.1103/PhysRevLett.69.1395
[89]	Zhong D, Franke J-H, Podiyanachari S K, Blmker T, Zhang H, Kehr G, Erker G, Fuchs H, Chi L 2011 Linear alkane polymerization on a gold surface Science 334 213-6 doi: 10.1126/science.1211836
[90]	Li Q, et al 2016 Surface-controlled mono/diselective ortho C-H bond activation J. Am. Chem. Soc. 138 2809-14 doi: 10.1021/jacs.5b13286
[91]	Fan Q, Werner S, Tschakert J, Ebeling D, Schirmeisen A, Hilt G, Hieringer W, Gottfried J M 2018 Precise monoselective aromatic C-H bond activation by chemisorption of meta-aryne on a metal surface J. Am. Chem. Soc. 140 7526-32 doi: 10.1021/jacs.8b01658
[92]	Sun Q, Zhang C, Kong H, Tan Q, Xu W 2014 On-surface aryl-aryl coupling via selective C-H activation Chem. Commun. 50 11825-8 doi: 10.1039/C4CC05482B
[93]	Zhang C, Sun Q, Chen H, Tan Q, Xu W 2015 Formation of polyphenyl chains through hierarchical reactions: Ullmann coupling followed by cross-dehydrogenative coupling Chem. Commun. 51 495-8 doi: 10.1039/C4CC07953A
[94]	Hao Z, et al 2022 Converting n-alkanol to conjugated polyenal on Cu(110) surface at mild temperature J. Phys. Chem. Lett. 13 3276-82 doi: 10.1021/acs.jpclett.2c00369
[95]	Li X, et al 2021 Direct transformation of n-alkane into all-trans conjugated polyene via cascade dehydrogenation Natl Sci. Rev. 8 nwab093 doi: 10.1093/nsr/nwab093
[96]	Hao Z, et al 2022 From n-alkane to polyacetylene on Cu (110): linkage modulation in chain growth Sci. China Chem. 65 733-9 doi: 10.1007/s11426-021-1213-2
[97]	Guo W, et al 2022 Visualization of on-surface ethylene polymerization through ethylene insertion Science 375 1188-91 doi: 10.1126/science.abi4407
[98]	Okawa Y, Aono M 2001 Nanoscale control of chain polymerization Nature 409 683-4 doi: 10.1038/35055625
[99]	Okawa Y, Aono M 2001 Linear chain polymerization initiated by a scanning tunneling microscope tip at designated positions J. Chem. Phys. 115 2317-22 doi: 10.1063/1.1384554
[100]	Miura A, De Feyter S, Abdel-Mottaleb M M S, Gesquire A, Grim P C M, Moessner G, Sieffert M, Klapper M, Mllen K, De Schryver F C 2003 Light- and STM-tip-induced formation of one-dimensional and two-dimensional organic nanostructures Langmuir 19 6474-82 doi: 10.1021/la027051p
[101]	Sun Q, et al 2016 Bottom-up synthesis of metalated carbyne J. Am. Chem. Soc. 138 1106-9 doi: 10.1021/jacs.5b10725
[102]	Yu X, Li X, Lin H, Liu M, Cai L, Qiu X, Yang D, Fan X, Qiu X, Xu W 2020 Bond-scission-induced structural transformation from cumulene to diyne moiety and formation of semiconducting organometallic polyyne J. Am. Chem. Soc. 142 8085-9 doi: 10.1021/jacs.0c01925
[103]	Gao W, Kang F, Qiu X, Yi Z, Shang L, Liu M, Qiu X, Luo Y, Xu W 2022 On-surface debromination of C₆Br₆: C₆ ring versus C₆ chain ACS Nano 16 6578-84 doi: 10.1021/acsnano.2c00945
[104]	Yu X, et al 2022 Lattice-directed selective synthesis of acetylenic and diacetylenic organometallic polyynes Chem. Mater. 34 1770-7 doi: 10.1021/acs.chemmater.1c04015
[105]	Wang S, et al 2019 On-surface synthesis and characterization of individual polyacetylene chains Nat. Chem. 11 924-30 doi: 10.1038/s41557-019-0316-8
[106]	Wang C, Batsanov A S, Bryce M R, Martn S, Nichols R J, Higgins S J, Garca-Surez V M, Lambert C J 2009 Oligoyne single molecule wires J. Am. Chem. Soc. 131 15647-54 doi: 10.1021/ja9061129
[107]	Pavliek N, Schuler B, Collazos S, Moll N, Prez D, Guitin E, Meyer G, Pea D, Gross L 2015 On-surface generation and imaging of arynes by atomic force microscopy Nat. Chem. 7 623-8 doi: 10.1038/nchem.2300
[108]	Schuler B, Fatayer S, Mohn F, Moll N, Pavliek N, Meyer G, Pea D, Gross L 2016 Reversible Bergman cyclization by atomic manipulation Nat. Chem. 8 220-4 doi: 10.1038/nchem.2438
[109]	Pavliek N, Majzik Z, Collazos S, Meyer G, Prez D, Guitin E, Pea D, Gross L 2017 Generation and characterization of a meta-aryne on Cu and NaCl surfaces ACS Nano 11 10768-73 doi: 10.1021/acsnano.7b06137
[110]	de Oteyza D G, et al 2013 Direct imaging of covalent bond structure in single-molecule chemical reactions Science 340 1434-7 doi: 10.1126/science.1238187
[111]	Repp J, Meyer G, Stojkovi S M, Gourdon A, Joachim C 2005 Molecules on insulating films: scanning-tunneling microscopy imaging of individual molecular orbitals Phys. Rev. Lett. 94 26803 doi: 10.1103/PhysRevLett.94.026803
[112]	Albrecht F, Rey D, Fatayer S, Schulz F, Prez D, Pea D, Gross L 2020 Intramolecular coupling of terminal alkynes by atom manipulation Angew. Chem., Int. Ed. 59 22989-93 doi: 10.1002/anie.202009200
[113]	Repp J, Meyer G, Paavilainen S, Olsson F E, Persson M 2006 Imaging bond formation between a gold atom and pentacene on an insulating surface Science 312 1196-9 doi: 10.1126/science.1126073
[114]	Liljeroth P, Repp J, Meyer G 2007 Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules Science 317 1203-6 doi: 10.1126/science.1144366
[115]	Morgenstern K, Lorente N, Rieder K-H 2013 Controlled manipulation of single atoms and small molecules using the scanning tunnelling microscope Phys. Status Solidi b 250 1671-751 doi: 10.1002/pssb.201248392
[116]	Hla S-W, Bartels L, Meyer G, Rieder K-H 2000 Inducing all steps of a chemical reaction with the scanning tunneling microscope tip: towards single molecule engineering Phys. Rev. Lett. 85 2777-80 doi: 10.1103/PhysRevLett.85.2777
[117]	Zhong Q, Ihle A, Ahles S, Wegner H A, Schirmeisen A, Ebeling D 2021 Constructing covalent organic nanoarchitectures molecule by molecule via scanning probe manipulation Nat. Chem. 13 1133-9 doi: 10.1038/s41557-021-00773-4
[118]	Rizzo D J, Veber G, Jiang J, McCurdy R, Cao T, Bronner C, Chen T, Louie S G, Fischer F R, Crommie M F 2020 Inducing metallicity in graphene nanoribbons via zero-mode superlattices Science 369 1597-603 doi: 10.1126/science.aay3588
[119]	Fan Q, et al 2021 Biphenylene network: a nonbenzenoid carbon allotrope Science 372 852-6 doi: 10.1126/science.abg4509
[120]	Blackwell R E, Zhao F, Brooks E, Zhu J, Piskun I, Wang S, Delgado A, Lee Y-L, Louie S G, Fischer F R 2021 Spin splitting of dopant edge state in magnetic zigzag graphene nanoribbons Nature 600 647-52 doi: 10.1038/s41586-021-04201-y
[121]	Wang T, et al 2022 Magnetic interactions between radical pairs in chiral graphene nanoribbons Nano Lett. 22 164-71 doi: 10.1021/acs.nanolett.1c03578
[122]	Yang L, Park C-H, Son Y-W, Cohen M L, Louie S G 2007 Quasiparticle energies and band gaps in graphene nanoribbons Phys. Rev. Lett. 99 186801 doi: 10.1103/PhysRevLett.99.186801
[123]	Talirz L, Ruffieux P, Fasel R 2016 On-surface synthesis of atomically precise graphene nanoribbons Adv. Mater. 28 6222-31 doi: 10.1002/adma.201505738
[124]	Cai J, et al 2010 Atomically precise bottom-up fabrication of graphene nanoribbons Nature 466 470-3 doi: 10.1038/nature09211
[125]	Ruffieux P, et al 2016 On-surface synthesis of graphene nanoribbons with zigzag edge topology Nature 531 489-92 doi: 10.1038/nature17151
[126]	Berdonces-Layunta A, Schulz F, Aguilar-Galindo F, Lawrence J, Mohammed M S G, Muntwiler M, Lobo-Checa J, Liljeroth P, de Oteyza D G 2021 Order from a mess: the growth of 5-armchair graphene nanoribbons ACS Nano 15 16552-61 doi: 10.1021/acsnano.1c06226
[127]	Snchez-Snchez C, Dienel T, Deniz O, Ruffieux P, Berger R, Feng X, Mllen K, Fasel R 2016 Purely armchair or partially chiral: noncontact atomic force microscopy characterization of dibromo-bianthryl-based graphene nanoribbons grown on Cu(111) ACS Nano 10 8006-11 doi: 10.1021/acsnano.6b04025
[128]	de Oteyza D G, et al 2016 Substrate-independent growth of atomically precise chiral graphene nanoribbons ACS Nano 10 9000-8 doi: 10.1021/acsnano.6b05269
[129]	Cai J, et al 2014 Graphene nanoribbon heterojunctions Nat. Nanotechnol. 9 896-900 doi: 10.1038/nnano.2014.184
[130]	Kawai S, Saito S, Osumi S, Yamaguchi S, Foster A S, Spijker P, Meyer E 2015 Atomically controlled substitutional boron-doping of graphene nanoribbons Nat. Commun. 6 8098 doi: 10.1038/ncomms9098
[131]	Zhang Y, et al 2022 On-surface synthesis of a nitrogen-doped graphene nanoribbon with multiple substitutional sites Angew. Chem., Int. Ed. 61 e202204736 doi: 10.1002/anie.202204736
[132]	Moreno C, et al 2018 Bottom-up synthesis of multifunctional nanoporous graphene Science 360 199-203 doi: 10.1126/science.aar2009
[133]	Tenorio M, Moreno C, Febrer P, Castroesteban J, Ordejn P, Pea D, Pruneda M, Mugarza A 2022 Atomically sharp lateral superlattice heterojunctions built-in nitrogen-doped nanoporous graphene Adv. Mater. 34 e2110099 doi: 10.1002/adma.202110099
[134]	Chen Y-C, de Oteyza D G, Pedramrazi Z, Chen C, Fischer F R, Crommie M F 2013 Tuning the band gap of graphene nanoribbons synthesized from molecular precursors ACS Nano 7 6123-8 doi: 10.1021/nn401948e
[135]	Talirz L, et al 2017 On-surface synthesis and characterization of 9-atom wide armchair graphene nanoribbons ACS Nano 11 1380-8 doi: 10.1021/acsnano.6b06405
[136]	Ruffieux P, et al 2012 Electronic structure of atomically precise graphene nanoribbons ACS Nano 6 6930-5 doi: 10.1021/nn3021376
[137]	Rizzo D J, Veber G, Cao T, Bronner C, Chen T, Zhao F, Rodriguez H, Louie S G, Crommie M F, Fischer F R 2018 Topological band engineering of graphene nanoribbons Nature 560 204-8 doi: 10.1038/s41586-018-0376-8
[138]	Grning O, et al 2018 Engineering of robust topological quantum phases in graphene nanoribbons Nature 560 209-13 doi: 10.1038/s41586-018-0375-9
[139]	Cao T, Zhao F, Louie S G 2017 Topological phases in graphene nanoribbons: junction states, spin centers, and quantum spin chains Phys. Rev. Lett. 119 76401 doi: 10.1103/PhysRevLett.119.076401
[140]	Rizzo D J, et al 2021 Rationally designed topological quantum dots in bottom-up graphene nanoribbons ACS Nano 15 20633-42 doi: 10.1021/acsnano.1c09503
[141]	Li S, Liu M, Qiu X 2020 Scanning probe microscopy of topological structure induced electronic states of graphene Small Methods 4 1900683 doi: 10.1002/smtd.201900683
[142]	Liu M, et al 2017 Graphene-like nanoribbons periodically embedded with four- and eight-membered rings Nat. Commun. 8 14924 doi: 10.1038/ncomms14924
[143]	Liu M, Liu M, Zha Z, Pan J, Qiu X, Li T, Wang J, Zheng Y, Zhong D 2018 Thermally induced transformation of nonhexagonal carbon rings in graphene-like nanoribbons J. Phys. Chem. C 122 9586-92 doi: 10.1021/acs.jpcc.8b02565
[144]	Li D-Y, et al 2021 Ladder phenylenes synthesized on Au(111) surface via selective [2+2] cycloaddition J. Am. Chem. Soc. 143 12955-60 doi: 10.1021/jacs.1c05586
[145]	Fan Q, Martin-Jimenez D, Ebeling D, Krug C K, Brechmann L, Kohlmeyer C, Hilt G, Hieringer W, Schirmeisen A, Gottfried J M 2019 Nanoribbons with nonalternant topology from fusion of polyazulene: carbon allotropes beyond graphene J. Am. Chem. Soc. 141 17713-20 doi: 10.1021/jacs.9b08060
[146]	de la Torre B, et al 2020 Tailoring -conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers Nat. Commun. 11 4567 doi: 10.1038/s41467-020-18371-2
[147]	Di Giovannantonio M, Urgel J I, Beser U, Yakutovich A V, Wilhelm J, Pignedoli C A, Ruffieux P, Narita A, Mllen K, Fasel R 2018 On-surface synthesis of indenofluorene polymers by oxidative five-membered ring formation J. Am. Chem. Soc. 140 3532-6 doi: 10.1021/jacs.8b00587
[148]	Sun Q, et al 2018 Direct formation of C-C triple-bonded structural motifs by on-surface dehalogenative homocouplings of tribromomethyl-substituted arenes Angew. Chem., Int. Ed. 57 4035-8 doi: 10.1002/anie.201801056
[149]	SnchezGrande A, et al 2019 On-surface synthesis of ethynylene-bridged anthracene polymers Angew. Chem., Int. Ed. 58 6559-63 doi: 10.1002/anie.201814154
[150]	Sun K, Sagisaka K, Peng L, Watanabe H, Xu F, Pawlak R, Meyer E, Okuda Y, Orita A, Kawai S 2021 Head-to-tail oligomerization by silylene-tethered Sonogashira coupling on Ag(111) Angew. Chem., Int. Ed. 60 19598-603 doi: 10.1002/anie.202102882
[151]	Kawai S, et al 2022 On-surface synthesis of porphyrin-complex multi-block co-oligomers by defluorinative coupling Angew. Chem., Int. Ed. 61 e202114697 doi: 10.1002/anie.202114697
[152]	Sun Q, Cai L, Ma H, Yuan C, Xu W 2016 Dehalogenative homocoupling of terminal alkynyl bromides on Au(111): incorporation of acetylenic scaffolding into surface nanostructures ACS Nano 10 7023-30 doi: 10.1021/acsnano.6b03048
[153]	Kawai S, Krej O, Foster A S, Pawlak R, Xu F, Peng L, Orita A, Meyer E 2018 Diacetylene linked anthracene oligomers synthesized by one-shot homocoupling of trimethylsilyl on Cu(111) ACS Nano 12 8791-7 doi: 10.1021/acsnano.8b05116
[154]	SnchezGrande A, et al 2020 Diradical organic one-dimensional polymers synthesized on a metallic surface Angew. Chem., Int. Ed. 59 17594-9 doi: 10.1002/anie.202006276
[155]	Zhang C, Jaculbia R B, Tanaka Y, Kazuma E, Imada H, Hayazawa N, Muranaka A, Uchiyama M, Kim Y 2021 Chemical identification and bond control of -skeletons in a coupling reaction J. Am. Chem. Soc. 143 9461-7 doi: 10.1021/jacs.1c02624
[156]	Urgel J I, et al 2020 On-surface synthesis of cumulene-containing polymers via two-step dehalogenative homocoupling of dibromomethylene-functionalized tribenzoazulene Angew. Chem., Int. Ed. 59 13281-7 doi: 10.1002/anie.202001939
[157]	Cirera B, et al 2020 Tailoring topological order and -conjugation to engineer quasi-metallic polymers Nat. Nanotechnol. 15 437-43 doi: 10.1038/s41565-020-0668-7
[158]	Zhong Q, Niu K, Chen L, Zhang H, Ebeling D, Bjrk J, Mllen K, Schirmeisen A, Chi L 2022 Substrate-modulated synthesis of metal-organic hybrids by tunable multiple aryl-metal bonds J. Am. Chem. Soc. 144 8214-22 doi: 10.1021/jacs.2c01338
[159]	Fan Q, Wang T, Dai J, Kuttner J, Hilt G, Gottfried J M, Zhu J 2017 On-surface pseudo-high-dilution synthesis of macrocycles: principle and mechanism ACS Nano 11 5070-9 doi: 10.1021/acsnano.7b01870
[160]	Kolmer M, Zuzak R, Steiner A K, Zajac L, Engelund M, Godlewski S, Szymonski M, Amsharov K 2019 Fluorine-programmed nanozipping to tailored nanographenes on rutile TiO₂ surfaces Science 363 57-60 doi: 10.1126/science.aav4954
[161]	Zhan G, Cai Z-F, Strutyski K, Yu L, Herrmann N, Martnez-Abada M, Melle-Franco M, Mateo-Alonso A, De Feyter S 2022 Observing polymerization in 2D dynamic covalent polymers Nature 603 835-40 doi: 10.1038/s41586-022-04409-6
[162]	Lu C, Mo Y-P, Hong Y, Chen T, Yang Z-Y, Wan L-J, Wang D 2020 On-surface growth of single-layered homochiral 2D covalent organic frameworks by steric hindrance strategy J. Am. Chem. Soc. 142 14350-6 doi: 10.1021/jacs.0c06468
[163]	Liu X-H, Guan C-Z, Ding S-Y, Wang W, Yan H-J, Wang D, Wan L-J 2013 On-surface synthesis of single-layered two-dimensional covalent organic frameworks via solid-vapor interface reactions J. Am. Chem. Soc. 135 10470-4 doi: 10.1021/ja403464h
[164]	Dienstmaier J F, Medina D D, Dogru M, Knochel P, Bein T, Heckl W M, Lackinger M 2012 Isoreticular two-dimensional covalent organic frameworks synthesized by on-surface condensation of diboronic acids ACS Nano 6 7234-42 doi: 10.1021/nn302363d
[165]	Liu X-H, Guan C-Z, Wang D, Wan L-J 2014 Graphene-like single-layered covalent organic frameworks: synthesis strategies and application prospects Adv. Mater. 26 6912-20 doi: 10.1002/adma.201305317
[166]	Zhang R, et al 2013 Chemical mapping of a single molecule by plasmon-enhanced Raman scattering Nature 498 82-86 doi: 10.1038/nature12151
[167]	Wang R-P, et al 2021 Raman detection of bond breaking and making of a chemisorbed up-standing single molecule at single-bond level J. Phys. Chem. Lett. 12 1961-8 doi: 10.1021/acs.jpclett.1c00074
[168]	Xu J, et al 2021 Determining structural and chemical heterogeneities of surface species at the single-bond limit Science 371 818-22 doi: 10.1126/science.abd1827
[169]	Kazuma E, Jung J, Ueba H, Trenary M, Kim Y 2017 Direct pathway to molecular photodissociation on metal surfaces using visible light J. Am. Chem. Soc. 139 3115-21 doi: 10.1021/jacs.6b12680
[170]	Yu M, et al 2020 Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition Nat. Chem. 12 1035-41 doi: 10.1038/s41557-020-0540-2
[171]	Nacci C, Baroncini M, Credi A, Grill L 2018 Reversible photoswitching and isomer-dependent diffusion of single azobenzene tetramers on a metal surface Angew. Chem., Int. Ed. 57 15034-9 doi: 10.1002/anie.201806536
[172]	Galanti A, Diez-Cabanes V, Santoro J, Valek M, Minoia A, Mayor M, Cornil J, Samor P 2018 Electronic decoupling in C₃-symmetrical light-responsive tris(azobenzene) scaffolds: self-assembly and multiphotochromism J. Am. Chem. Soc. 140 16062-70 doi: 10.1021/jacs.8b06324
[173]	Zhang X, Xu S, Li M, Shen Y, Wei Z, Wang S, Zeng Q, Wang C 2012 Photo-induced polymerization and isomerization on the surface observed by scanning tunneling microscopy J. Phys. Chem. C 116 8950-5 doi: 10.1021/jp2115884
[174]	Kazuma E, Jung J, Ueba H, Trenary M, Kim Y 2018 Real-space and real-time observation of a plasmon-induced chemical reaction of a single molecule Science 360 521-6 doi: 10.1126/science.aao0872
[175]	Kazuma E, Lee M, Jung J, Trenary M, Kim Y 2020 Single-molecule study of a plasmon-induced reaction for a strongly chemisorbed molecule Angew. Chem., Int. Ed. 59 7960-6 doi: 10.1002/anie.202001863
[176]	Bckmann H, Gawinkowski S, Waluk J, Raschke M B, Wolf M, Kumagai T 2018 Near-field enhanced photochemistry of single molecules in a scanning tunneling microscope junction Nano Lett. 18 152-7 doi: 10.1021/acs.nanolett.7b03720
[177]	Mahapatra S, Schultz J F, Li L, Zhang X, Jiang N 2022 Controlling localized plasmons via an atomistic approach: attainment of site-selective activation inside a single molecule J. Am. Chem. Soc. 144 2051-5 doi: 10.1021/jacs.1c11547
[178]	Tanaka H, Kawai T 2009 Partial sequencing of a single DNA molecule with a scanning tunnelling microscope Nat. Nanotechnol. 4 518-22 doi: 10.1038/nnano.2009.155
[179]	Saywell A, Sprafke J K, Esdaile L J, Britton A J, Rienzo A, Anderson H L, O’Shea J N, Beton P H 2010 Conformation and packing of porphyrin polymer chains deposited using electrospray on a gold surface Angew. Chem., Int. Ed. 49 9136-9 doi: 10.1002/anie.201004896
[180]	O’Sullivan M C, et al 2011 Vernier templating and synthesis of a 12-porphyrin nano-ring Nature 469 72-75 doi: 10.1038/nature09683
[181]	McCurdy R D, Jacobse P H, Piskun I, Veber G C, Rizzo D J, Zuzak R, Mutlu Z, Bokor J, Crommie M F, Fischer F R 2021 Synergetic bottom-up synthesis of graphene nanoribbons by matrix-assisted direct transfer J. Am. Chem. Soc. 143 4174-8 doi: 10.1021/jacs.1c01355
[182]	Loth S, Etzkorn M, Lutz C P, Eigler D M, Heinrich A J 2010 Measurement of fast electron spin relaxation times with atomic resolution Science 329 1628-30 doi: 10.1126/science.1191688
[183]	Terada Y, Yoshida S, Takeuchi O, Shigekawa H 2010 Real-space imaging of transient carrier dynamics by nanoscale pump-probe microscopy Nat. Photon. 4 869-74 doi: 10.1038/nphoton.2010.235
[184]	Cocker T L, Peller D, Yu P, Repp J, Huber R 2016 Tracking the ultrafast motion of a single molecule by femtosecond orbital imaging Nature 539 263-7 doi: 10.1038/nature19816
[185]	Wiesendanger R, Gntherodt H, Gntherodt G, Gambino R J, Ruf R 1990 Observation of vacuum tunneling of spin-polarized electrons with the scanning tunneling microscope Phys. Rev. Lett. 65 247-50 doi: 10.1103/PhysRevLett.65.247
[186]	Wiesendanger R 2009 Spin mapping at the nanoscale and atomic scale Rev. Mod. Phys. 81 1495-550 doi: 10.1103/RevModPhys.81.1495
[187]	Yamamoto S, Imada H, Kim Y 2022 Atomic-scale photon mapping revealing spin-current relaxation Phys. Rev. Lett. 128 206804 doi: 10.1103/PhysRevLett.128.206804
[188]	Zhong J-H, Jin X, Meng L, Wang X, Su H-S, Yang Z-L, Williams C T, Ren B 2017 Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution Nat. Nanotechnol. 12 132-6 doi: 10.1038/nnano.2016.241
[189]	Lee J, Crampton K T, Tallarida N, Apkarian V A 2019 Visualizing vibrational normal modes of a single molecule with atomically confined light Nature 568 78-82 doi: 10.1038/s41586-019-1059-9
[190]	Jaculbia R B, Imada H, Miwa K, Iwasa T, Takenaka M, Yang B, Kazuma E, Hayazawa N, Taketsugu T, Kim Y 2020 Single-molecule resonance Raman effect in a plasmonic nanocavity Nat. Nanotechnol. 15 105-10 doi: 10.1038/s41565-019-0614-8
[191]	Yin H, et al 2020 Nanometre-scale spectroscopic visualization of catalytic sites during a hydrogenation reaction on a Pd/Au bimetallic catalyst Nat. Catal. 3 834-42 doi: 10.1038/s41929-020-00511-y
[192]	Schultz J F, Li S, Jiang S, Jiang N 2020 Optical scanning tunneling microscopy based chemical imaging and spectroscopy J. Phys.: Condens. Matter 32 463001 doi: 10.1088/1361-648X/aba8c7
[193]	Nonnenmacher M, O’Boyle M P, Wickramasinghe H K 1991 Kelvin probe force microscopy Appl. Phys. Lett. 58 2921-3 doi: 10.1063/1.105227
[194]	Castaeda-Uribe O A, Reifenberger R, Raman A, Avila A 2015 Depth-sensitive subsurface imaging of polymer nanocomposites using second harmonic Kelvin probe force microscopy ACS Nano 9 2938-47 doi: 10.1021/nn507019c